Process for breaking petroleum emulsions



Patented Jan. 27, 1953 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, a corporation of Delaware No Drawing. Application May 14, 1951, Serial No. 226,302

9 Claims.

This invention relates to petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

One object of my invention is to provide a novel process for breaking or resolving emulsions of the kind referred to.

Another object of my invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, are of significant value in removing impurities particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous com ponent which would or might subsequently become either phase of the emulsion, in absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

The demulsifying agent employed in the present process is the fractional ester obtained from a polycarboxy acid and a nitrogen-containing diol obtained by the oxypropylation of methyl diethanolamine. Furthermore, the dihydroxylated compound prior to esterification must be waterin-soluble and kerosene-soluble. Momentarily ignoring certain variants of structure which will be considered subsequently the demulsifier may be exemplified by the following formula:

0 H II in which n and n are whole numbers with the proviso that 11 plus to equals a sum varying from 15 to 80; n is a whole number not over 2 and R is the radical of the polycarboxy acid /COOH R (COOH),."

and preferably free from any radicals having more than 8 uninterrupted carbon atoms in a single group, and with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble and kerosene-soluble.

Attention is directed to the co-pending application of C. M. Blair, Jr., Serial No. 70,811, filed January 13, 19%9 (now Patent 2,562,878, granted August 7, 1951), in which there is described, among other things, a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of an esterification product of a dicarboxylic acid and a polyalkylene glycol in which the ratio of equivalents of polybasic acid to equivalents of. polyalkylene glycol is in the range of 0.5 to 2.0, in which the alkylene group has from 2 to 3 carbon atoms, and in which the molecular weight of the product is between 1,500 to 4,000.

Similarly, there have been used esters of dicarboxy acids and polypropylene glycols in which 2 moles of the dicarboxy acid ester have been reacted with one mole of a polypropylene glycol having a molecular weight, for example, of 2,000 so as to form an acidic fractional ester. Subsequent examination of What is said herein in comparison with the previous examples as well as the hereto appended claims will show the line of delineation between such somewhat comparable compounds. Of greater significance, however, is What is said subsequently in regard to the structure of the parent diol as compared to polypropylene glycols whose molecular weights may vary from 1,000 to 2,000.

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is concerned with the preparation of the oxypropylation derivative of methyl diethanolamine;

Part 2 is concerned with the preparation of the esters from the oxypropylated derivatives;

Part 3 is concerned with the structure of the oxypropylation products obtained from the specified tertiary amine. Insofar that such materials are dihydroxylated there is a relationship to ordinary diols which do not contain a nitrogen atom, all of which is considered briefly in this particular part;

Part 4 is concerned with the use of the products herein described as demulsifiers for breaking water-in-oil emulsions; and I Part 5 is concerned with certain derivatives which can be obtained from the oxypropylated methyl diethanolamine. In some instances such derivatives are obtained by modest oxyethylation preceding the oxypropylation step, or oxypropylation followed by oxyethylation. This results in diols having somewhat different properties which can then be reacted with the same polycarboxy acids or anhydrides described in Part 3 to give effective demulsifying agents. For this reason a description of the apparatus makes casual mention of oxyethylation. For the same reason there is brief mention of the use of glycide.

PART 1 For a number of well known reasons equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not as a rule designed for a particular alkylene oxide. Invariably and inevitably, however, or particularly in the case of laboratory equipment and pilot plant size the design is such as to use any of the customarily available alkylene oxides, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. In the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of cat' alyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure'during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 200 pounds per square inch. They can be conducted also at temperatures approximating the boiling point of water or slightly above, as for example 95 to 120 C. Under such circumstances the pressure will be less than 30 pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife et a1., dated September 7, 1948. Low temperature, low pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric a1cohols,'glyco1s and triols.

Although the word glycol or diol is usually applied to compounds containing carbon, hydrogen, and oxygen only, yet the nitrogencontaining compounds herein are diols in the sense that they are dihydroxylated. Thus, the conditions which apply to the oxypropylation of certain glycols also apply in this instance.

'Since low pressure-low temperature-low-reaction-speed oxypropylations require considerable time, for instance, 1 to 7 days of 24 hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment ,with two added automatic features; (a) a solenoid controlled valve which shuts off the propylene oxid in event that the temperature gets outside a predetermined andset range, for instance, 95 to 120 C., and (b) another solenoid valve which shuts oiT the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxyalkylation whether it be oxypropylation or oxyethylation. With certain obvious changes the equipment can be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity or" approximately 15 gallons and a Working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as a cooling jacket, and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water and furtherequipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyalkylation procedures. In some instances in exploratory preparations an autoclave having a smaller capacity, for instance, approximately 3% liters in one case and about 1% gallons in another case, Was used.

Continuous operation, or substantially continuous operation, was achieved by the use of a separate container to hold th alkylene oxide being employed, particularly propylene oxide. In conjunction with the smaller autoclaves, the container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances a larger bomb was used, to wit, one having a capacity of about one gallon. This bomb was equipped, also, with an inlet for charging, and an eductor tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. A bomb having a capacity of about 60 pounds was used in connection with the l5-gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

Attention is directed again to what has been said previously in regard to automatic controls which shut ofi the propylene oxide in event temperature .of reaction passes out of the predeterminedrange or if pressure in the autoclave passes out of predetermined range.

With this particular arrangement practically all oxypropylations become uniform in that the reaction temperature was held Within a few degrees of any selected point, for instance, if 105 C. was selected as th operating temperature the maximum point would be at the most 110 C. or 1 2 C., and the lower point would be 95 or possibly 98 C. Similarly, the pressure was held at approximately 30 pounds maximum within a 5-pound variation one way or the other, but might drop to practically zero, especially where no solvent such asxylene is employed. The speed of reaction was comparatively slow under such conditions as compared with oxyalkylations at 200 C. Numerous reactions were conducted in which the time varied from one day (24 hours) up to three days (72 hours), for completion of the final member of a series. In some instances the reaction may take place in considerably less time, i. e., 24 hours or less, as far as a partial oxypropylation is concerned. The minimum time recorded was about a 3-hour period in a single step. Reactions indicated as being complete in hours may have been complete in a lesser period of time in light of the automatic equipment employed. This applies also where the reactions were complete in a shorter period of time, for instance, 4 to 5 hours. In the addition of propylene oxide, in the autoclave equipment as far as possible the valves were set so all the propylene oxide if fed continuously would be added at a rate so that the predetermined amount would react within the first hours of the 24-hour period or two-thirds of any shorter period. This meant that if the reaction was interrupted automatically for a period of time for pressure to drop or temperature to drop the predetermined amount of oxide would still be added in most instances well within the predetermined time period. Sometimes where the addition was a comparatively small amount in a 10-hour period there would be an unquestionable speeding up of the reaction, by simply repeating the examples and using 3, 4, or 5 hours instead of 10 hours.

When operating at a comparatively high temperature, for instance, between 150 to 200 C., an unreacted alkylene oxide such as propylene oxide, makes its presence felt in the increase in pressure or the consistency of a higher pressure. However, at a low enough temperature it may happen that the propylene oxide goes in as a liquid. If so, and if it remains unreacted there is. of course, an inherent danger and appropriate steps must be taken to safeguard against this possibility; if need be a sample must be withdrawn and examined for unreacted propylene oxide. One obvious procedure, of course, is to oxyprcpylate at a modestly higher temperature, for instance, at 140 to 150 C. Unreacted oxide affects determination of the acetyl or hydroxyl value of the hydroxylated compound obtained.

The higher the molecular weight of the compound, i. e., towards the latter stages of reaction, the longer the time required to add a given amount of oxide. One possible explanation is that the molecule, being larger, the opportunity for random reaction is decreased. Inversely, the lower the molecular weight the faster the reaction takes place. For this reason, sometimes at least, increasing the concentration of the catalyst does not appreciably speed up the reaction, particularly when the product subjected to oxyalweight. However, as has been pointed out previously, operating at a low pressure and a lowtemperature even in large scale operations as much as a week or ten days time may lapse to obtain some of the higher molecular weight derivatives from monohydric or dihydric materials.

In a number of operations the counterbalance scale or dial scale holding the propylene oxide bomb was so set that when the predetermined amount of propylene oxide had passed into the reaction the scale movement through a time operating device was set for either one to two hours so that reaction continued for 1 to 3 hours after the final addition of the last propylene oxide and thereafter the operation was shut down. This particular device is particularly suitable for use on larger equipment than laboratory size autoclaves, to wit, on semi-pilot plant or pilot plant size, as well as on large scale size. This final stirring period is intended to avoid the presence of unreacted oxide.

In this sort of operation, of course, the temperature range was controlled automatically by either use of cooling water, steam, or electrical heat, so as to raise or lower the temperature. The pressuring of the propylene oxide into the reaction vessel was also automatic insofar that the feed streams was set for a slow continuous run which was shut off in case the pressure passed a predetermined point as previously set out. All the points of design, construction, etc., were conventional including the gauges, check valves and entire equipment. As far as I am aware at least two firms, and possibly three, specialize in autoclave equipment such as I have employed in the laboratory, and are prepared to furnish equipment of this same kind. Similarly pilot plant equipment is available. This point is simply made as a precaution in the direction of safety. Oxyalkylations, particularly involving ethylene oxide, glycide, propylene oxide, etc., should not be conducted except in equipment specifically designed for the purpose.

Example 1 a The starting material was a commercia1 grade of methyl diethanolamine. Since this material is definitely basic the initial oxypropylation did not require the addition of a catalyst. A catalyst was added in subsequent oxypropylations as noted. The particular autoclave employed was one with a capacity of 1% gallons or so, or on the average of about 10 pounds of reaction mass. The speed of the stirrer could be varied from to 350 R. P. M. 3.94 pounds of methyl diethanolamine were charged into the autoclave. The reaction pot was flushed out with nitrogen. The autoclave was sealed and the automatic devices adjusted for injecting 6.31 pounds of propylene oxide in an hour. This time period had no particular significance in this instance for the reason that the reactant, being strongly basic, absorbed or reacted with propylene oxide practically as fast as it was added, The entire procedure required only about ten minutes. Similarly, the pressure regulator was set for a maximum of 32 pounds per square inch. Since the propylene oxide reacted with the amine practically as rapidly as added, there was no pressure. The initial introduction of the propylene oxide was not started until the heating devices had raised the temperature to about the boiling point of water. As previously pointed out, the reaction was complete in a substantially short period. The reactants .added was 41.5 pounds.

were too small in quantity to serve satisfactorily in a larger autoclave. However, at the end of this reaction when the oxypropylated product represented approximately pounds, there was no difficulty in the use of our larger autoclave and, thus the entire reaction mass was transferre to a larger autoclave having a l5-gallon capacity, or approximately 120 pounds of reaction mass. This large autoclave was employed in all subsequent examples, to wit, Examples 205 through 6a.

Example 2a.

As previously noted the entire reaction mass, identified as Example 1a, preceding, was transferred to a larger autoclave. This reaction mass represented 3.94 pounds of the amine and 6.31 pounds of propylene oxide. To this reaction mass there was added one pound of caustic soda. 43.75 pounds of propylene oxide were added. The oxypropylation was conducted in such a manner that the pressure gauge was set for 35 to 37 pounds maximum pressure and the temperature was set for 220 to 225 F. (moderately above the boiling point of water). Actually the bulk of the reaction could take place and probably did take place at a lower temperature. The time involved was a 3-hour period. The oxide was added at a rate of about 'pounds per hour, and thus there was a period at the end of the 3-hour time interval which represented merely stirring without addition of oxide. When the reaction was complete part of the mass was withdrawn and the remainder subjected to further oxypropylation as described in Example 3a, immediately following.

Example 30.

47 pounds of the reaction mass previously identified as Example 2a, preceding, and equivalent to 3.37 pounds of the amine, 42.78 pounds of propylene oxide, and .85 pound of caustic soda, were subjected to further oxypropylation with rate of about 12 or 13 pounds per hour. At the end of the reaction period part of the sample was withdrawn and the remainder of the reaction mass was subjected to further oxypropylation as is described in Example 5a, immediately following.

Example 5a Approximately 68.94 pounds of the reaction mass identified as Example 4a, preceding, and equivalent to 1.58 pounds of amine, 66.96 pounds of oxide and .4 pound of caustic soda, were subjected to further oxypropylation in the same manner as described in Examples 2a and 3a, preceding. The time period was the same, to wit, 4 hours. The amount of oxide added was 34.75 pounds. It was added at the rate of about 10 pounds per hour. At the end or the reaction period part of the sample was withdrawn and the remainder of the reaction mass was subjected again to further oxypropylation as described in Example 60., following.

Example 615 Approximately 69.19 pounds of the reaction mass, equivalent to 1.06 pounds of the amine, 67.86 pounds of the oxide, and .27 pound of caustic soda were subjected to further oxypropylation under the same conditions as described in the example immediately preceding. The reaction time was somewhat longer, to wit, 5 hours. The amount of oxide added was comparatively small, to wit, 15.75 pounds. It was added at the rate of about 4 pounds per hour.

In this particular series of examples the oxypropylations were stopped at this stage. In other series I have continued the oxypropylation so the theoretical molecular weight varied from 12,000 to 15,000 but the increase in molecular weight by hydroxyl determination was compara- Ziggey small, varying from 4300 to approximately TABLE 1 Composition Before Com osit'on p I at End M. W. Max. 11%;. A o d C t M ig Time 0. mine xi e a a- Theo. Amine Oxd O y Amt, Amt, lyst, M01. Amt, Am ti 9 P lbs. lbs lbs. Wt. 5 lbs. lbs.

lll 3.94 3. 94 6.31 220-225 2a 3.94 6.31 1.0 1, 530 3.94 50.06 1'0 305' 220-225 a 3.37 42.78 .85 2,580 3.37 81.28 .85 1,423 220-225 i 4.1," 2.34 57.32 .59 5,370 2.34 98.82 .59' 2,060 220-225 35-37 4 3 1. 5s 55. 96 .40 7,770 1.58 101.71 .40 3,040 220-225 35-37 4 6a 1.06 37.50 .27 9, 500 1.06 33.31 .27 3, 640 I220-225 35-37 5 Example 4:1

60.25 pounds of the reaction mass previously identified as Example 307, and equivalent to 2.34 pounds of the amine, 57.32 pounds of propylene oxide, and .59 pound of caustic soda, were subjected to further oxypropylation in the same manner as described in Example 2a, preceding. The time period was the same as in Example 30., preceding, to wit, 4 hours. The amount of oxide This was added at the Example 2a. was soluble in water, dispersible in xylene, and insoluble in kerosene; Example 311 was emulsifiable in water, soluble in xylene, and insoluble in kerosene; Examples 4a, 5a, and 6a were all insoluble in water, soluble in xylene, and soluble in kerosene. This was true, also, in regard to those products previously referred to which were of a higher molecular weight.

The final product, i. e., at the end of the oxypropylation step, was a pale to dark amber fluid with a mere suggestion of a reddish tint. This was more o-r less characteristic of all the various oxy-propylation products in the various stages. These products were, of course, slightly alkaline due to the residual caustic soda and also due to the basic nitrogen atom. The residual basicity due to the catalyst, of course, would be the same if sodium methylate had been used.

Speaking of insolubility in water or solubility 9. in kerosene such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds. This is indicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molccular weight calculated by usual methods on basis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds with a high degree of accuracy when the molecular Weights exceed 2,000. In some instances the acetyl value or hydroxyl value serves as satisfactorily as an index to the molecular weight as any other procedure, subject to the above limitations, and especially in the higher molecular weight range. If any difficulty is encountered in the manufacture of the esters as described in Part 2 the stoichiometrical amount of acid or acid compound should be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of common knowledge and requires no further elaboration. In fact, it is illustrated by some of the examples appearing in the patent previously-mentioned;

PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated derivatives described in Part 1, immediately preceding, and polycarboxy acids, particularly tricarboxy acids like citric and dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic' acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or anhydride ad'ducts as obtained by the Diels-Alder reaction from products such as maleic anhydride and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification: They may contain as many as 36 carbon atoms as,for example, the acids obtained by dimerization of unsaturated fatty acids, unsaturated monocarboxy fatty acids,

or unsaturated monocarboxy acids having 18: carbon atoms. Reference to the acid in: the hereto appended claims obviouslyincludes the anhydrides or any other obvious equivalents. preference, however, is to use polycarboxy acids having not over 8 carbon; atoms.

The production of esters including acid esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds is well known. Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional. procedure is employed. On a laboratory scale one can employ a resin-pot of the kind described in U. S. Patent No. 2,499,370, dated March '7, 1950 to De Groote and Keiser, and particularly with one or more opening to permit the use of a porous spreader if hydrochloric acid gas isto be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange the oxypropylated compounds, and particuiarly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such as diglycollic acid, which is strongly acidic there is no need to add any cata-- lyst. The use of hydrochloric acid gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of. removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever.

The products obtained in Part 1 preceding may contain a basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part l is then diluted further with sufficient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 45% solution. To this solution there is added a polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycollic acid, etc; The mixture is refluxed until esterification is complete as indicated by elimination of water or drop in carboxyl value. Needless to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycollic acid, for example, water is eliminated. All such procedures are conventional and have been so thoroughiy described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (suiiioient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear, somewhat vis- 11 It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality of both diol radicals and acid radicals; the product is characterized by having 12 tinued, and, of course, is at a high temperature, to wit, about 160 to 170 C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is only one diol radical. 5 an acid, water of reaction should appear and In some instances and, in fact, in many inshould be eliminated at the above reaction temstances I have found that in spite of the dehydraperature. If it is not eliminated I simply sepajtion methods employed above that a mere trace of rate out another or 20 cc. of benzene by means water still comes through and that this mere of the phase-separating trap and thus raise the trace of Water certainly interferes with the 10 temperature to 180 or 190 C., or even to 200 C., acetyl or hydroxyl value determination, at least if need be. My preference is not to go above when a number of conventional procedures are 200 C. used and may retard esterification, particularly The use of such solvent is extremely satisfacwhere there is no sulfonic acid or hydrochloric tory provided one does not attempt to remove acid present as a catalyst. Therefore, I have prethe solvent subsequently except by vacuum disferred to use the following procedure: I have emtillation and provided there is no objection to a ployed about 200 grams of the 01101 as described little residue. Actually, when these materials are in Part 1, preceding; I have added about 60 used for a purpose such as demulsification the grams o b n and then refluxed this mixture solvent might just as well be allowed to remain. the lass resin pot us phase-Separating If the solvent is to be removed by distillation, and p \mtll the benzene earned out all e Water particularly vacuum distillation, then the high f 5 Water of 59111171011 the eqwvelentboiling aromatic petroleum solvent might Well be Srdmanly rerfllux i teg pterature S 1 2 replaced by some more expensive solvent, such ai fi g g t o i g 150 as decalin or an alkylated decalin which has a f a 2 222 ig ggi g g i i ifi rather definite or close range boiling point. The or a little less benzene and then add the required g g z the i Z W 1S f namount of the carboxy reactant and also about V6 10 a proce u e a r quires e a 9 150 grams of a high boiling aromatic petroleum In h appnded solvefnt Whlch solvent. These solvents are sold by various oil 3 pears m an {Stances, 1s a mlxture of volumes refineries and, as far as solvent effect act as if of P aromatlc petroleum Solvent prevlously they were almost completely aromati i harscribed and 3 volumes of benzene. ThlS was used, acter. Typical distillation data in the particur a similar mix r in the m n r pr vi y "lar type I have employed and found very satisdescribed. In a large number of similar exfactory are the following: 5 amples decalin has been used but it is my prefer- I P B 3 C m1 8 C ence to use the above mentioned mixture and 5 m1" 5 m1" particularly Wlth the preliminary step of remov- 10 m1" 0 1 43 C. ing all the Water. If one does not intend to re- 15 ml., 215 C. ml., 252 C. move the solvent my preference is to use the pe- 20 ml., 216 C. '70 ml., 252 C. 40 troleum solvent-benzene mixture although ob- 25 ml., 220 C. '75 ml., 260 C. viously any of the other mixtures, such as decalin 225 C. 1 1 and xylene, can be employed. 35 ml., 230 C. 2 The data included in the subsequent tables,

0 o ,40 ml., 234 C. ml., 280 C- 1. 0., Tables 2 and 3, are self-explanatory, and 45 ml., 23 C. -1 307 45 very complete and it is believed no further elab- After this material is added, refluxing is conoration is necessary:

TABLE 2 Mol. Amt. i E 132. L'I/ihe/Vo. Agual wa g Poly? 3S6 A0013 o i of droiyl on gg Polycarboxy Reactant 322%? Ester Ompd H. C. H'C Value Actual m;

' V g (ar 2a 1,030 08.9 120 893 200 Diglycolic Acid 5 211 1,030 08.9 120 890 198 Phthalic Anhydride... 55.5 20 1,030 38.9 120 890 198 MalcicAnhydride 43, 20 1, 630 68.0 120 896 198 Citraconic Anhydride 49 5 20 1,030 08.9 120 896 199 Aconitic Acid 7 20 1,630 68.9 126 896 198 Oxalic Acid 55 30 2,580 43.5 78.8 1,420 202 Diglycolic Acid 30 2,580 43.5 78.8 1,420 202 Phthalic Anhydride 42 3a 2, 580 43.5 78.8 1, 426 203 Maleic Anhydride 27,8 30 2, 580 43.5 78.8 1,426 202 C-itraconic Anhydridc. 31 3 3a 2, 580 43.5 78.8 1, 426 203 Aconitic Acid 49 4 33 2,580 43.5 78.8 1,420 208 Oxalic Acid 40 5,370 20.9 54.5 2,000 203 Diglycolic Acid" 254 40 5,370 20.9 54.5 2,000 208 Phthalic Anhydr 300 40 5,370 20.9 54.5 2,000 208 Maleic Anhydride. 10,8 40 5,370 20.9 54.5 2, 060 208 Citraconic Anhydride 22,6 4a 5, 370 20.9 54.5 2,000 208 Aconiticllcid 5, 40 5,370 20.9 54.5 2,000 207 Oxalic Acid 50 7,770 14.4 36.8 3,040 205 Diglycolic Acid 1&0 5a 7, 770 14.4 36.8 3,040 204 Phthalic Anhydride 20,0 511 7, 770 14.4 30.8 3, 040 205 Maleic Anhydride 13, 50 7, 770 14.4 36.8 3, 040 203 Citraconic Anhydride 15,0 50 7, 770 14.4 36.8 3,040 204 Aconitic Acid. 23,3 50 7, 770 14.4 36.8 3,040 200 Oxalic Acid 60 9,500 11.8 30.8 3, 640 207 Diglycolic Acid 15,1 60 9,500 11.8 30.8 3,040 205 Phthalic Anhydr 611 9,500 11.8 30.8 3,040 200 Maleic Anhydride- 11,1 60 9,500 11.8 80.8 3,040 209 Citraconic Anhydridc... 12.9 60 9,500 11.8 30.8 3, 040 200 Aconitic Acid 1 60 9,500 11.8 30.8 3,040 205 Oxalic Acid 1 TABLE 3 Ex. N o. Amt. Esterifica- Time of Water of Acld Solvent Solvent tion Temp, Esterifica- Out Ester (grs) C. tion (hrs) (00.)

final cogeneric reaction mixture.

The procedure for manufacturing the esters has been illustrated by preceding examples. If for any reason reaction does not take place in a manner that is acceptable, attention should be directed to the following details: (a) Recheck the hydroxyl or acetyl value of the oxypropylated primary amines of the kind specified and use a stoichiometrically equivalent amount of acid; (b) if the reaction does not proceed with reasonable speed either raise the temperature indicated or else extend the period of time up to 12 or 16 hours if need be; (c) if necessary, use /2% of paratoluene sulfonic acid or some other acid as a catalyst; (d) if the esterification does not produce a clear product a check should be made to see if an inorganic salt such as sodium chloride or sodium sulfate is not precipitating out. Such salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal, as the size of the molecule increases and the reactive hydroxyl radical represents a smaller fraction of the entire molecule, more difficulty is involved in obtaining complete esterification.

Even under the most carefully controlled conditions of oxypropylation involving comparatively low temperatures and long time of reaction there are formed certain compounds whose composition is still obscure. Such side reaction products can contribute a substantial proportion of the Various suggestions have been made as to the nature of these compounds, such as being cyclic polymers of propylene oxide, dehydration products with the appearance of a vinyl radical, or isomers of propylene oxide or derivatives thereof, i. e., of an Even the determination of the hydroxyl value by conventional procedure leaves much to be desired due either to the cogeneric materials pre viously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale reddish amber to reddish black in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or the like color is not a factor and decolorization is not justified.

In the above instances I have permittedthe solvents to remain present in the final reaction mass. In other instances I have followed the same procedure using decalin or a mixture of decalin or benzene in the same manner and ultimately re-- moved all the solvents by vacuum distillation. Appearance of the final products are much the same as the diols before esterification and in some instances were somewhat darker in color and had a more reddish cast and perhaps somewhat more viscous.

PART 3 Previous reference has been made to the fact that diols (nitrogen-free compounds) such as polypropyleneglycol of approximately 2,000 molecular weight, for example, have been esterified with dicarboxy acids and employed as demulsifying agents. The herein described compounds are difierent from such diols although both, it is true, are high molecular weight dihydroxylated compounds. The instant compounds have present a nitrogen atom which is at least modestly basic. In any event, such nitrogen atom must in all likelihood influence the orientation of acidic molecules at an interface. Stated another way, the ultimate ester has at least two free carboxyl radicals. It seems reasonable to assume that the orientation of such molecules at an oil-water interface, for example, is affected by the presence of a nitrogen atom having significant or definite basicity. Regardless of what the difference may be the fact still remains that the compounds of the kind herein described may be, and frequently are, l( 15% or 20% better on a quantitative basis than the simpler compound previously described, and demulsify faster and give cleaner oil in many instances. The method of making such comparative tests has been described in a booklet entitled Treating Oil Field Emulsions, used in the Vocational Training Course, Petroleum Ingutstry Series, of the American Petroleum Insti- It may be well to emphasize also the fact that oxypropylation does not produce a single compound but a cogeneric mixture. The factor involved is the same as appears if one were oxypropylating a monohydric alcohol or a glycol. Momentarily, one may consider the structure of a ypr py ly o such as polypropylene glycol of 2060 molecular weight. Propylene glycol has a primary alcohol radical and a secondary alcohol radical. In this sense the building unit which forms polypropylene glycols is not symmetrical. Obviously, then, polypropylene glycols can be obtained, at least theoretically, in which two secondary alcohol groups are united or a second ary alcohol group is united to a primary alcohol group, etherization being involved, of course, in each instance.

- fisually no effort is made to differentiate between oxypropylation taking place, for example,

at the primary alcohol radical or the secondary alcohol radical. Actually, when such products are obtained, such as a high molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such at HO RO nH in which n has one and only one value, for instance, 14, 15 or 16, or

the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture. On a statistical basis, of course, 11 can be appropriately specified. For practical purposes one need only consider the oxypropylation of a .monohydric alcohol because in essence this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain 80% or 90% or 100% of such compound. However, in the case of at least monohydric initial reactants one can readily draw the formulas of a large number of compounds which appear in some of the probable mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by way of illustrating reference is made to the copending application of De Groote, Wirtel, and Pettingill, Serial No. 109,791, filed August 11, 1949 (now Patent 2,549,434, granted April 17, 1951).

However, momentarily referring again to a monohydric initial reactant it is obvious that if one selects any such simple hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxides except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 10, or 50 units. If such compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake of convenience, may be indicated as RO(C2H4O)30OH. Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following, RO(C2I-I4O)1LH,wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where n may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either proportion of the various members of touchin homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difficulty, it is necessary to resort to some other method of description, or else consider the value of 12., in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of the propylene oxide to the present or other specified amine is 30 to 1. Actually, one obtains products in which 11 probably varies from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture.

PART 4 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., maybe employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining if petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsiiying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon th emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsiiying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a emulsion while dripping, in the demu-lsifier'. d8: pending upon the convection. currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws; emulsion from, e. g., the, bottom of the tank, and reintroduces it into the top of the tank, the demulsifier being added, for example, at the suction, side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the wellhead and the final oil storage tank, by means of an adjustable proportioning mechanism or pro-,

portioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the fiow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing; quiescent settling of the chemicalized emulsion.

Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifler to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. cidedly useful when the demulsifier is used in connection with acidification of calcareous oilbearing strata, especially if suspended in or dis-. solved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small poportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural fiow or through special apparatus, with or without the. application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles from the mass.

The following is a typical installation.

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is, placed at the well-head where the effluent liquids leave the well. This reservoir or container. which may vary from gallons to 50 gallons for convenience, is connected to a proportioning pump. which in jects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold, amounts of fluid produced in 4 to 24 hours (-500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost, the very bottom so as. to. permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The

settling tank has two outlets, one being below the water level to drain oh the water resulting from demulsification or accompanying the emulsion as free water, the other being an oil outlet at the top to permit the passage of dehydrated This particular type of application is deoil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluid from the well to the settling tank, may include a sectionof pipe with baffles to serve as a mixer, to insure thorough distribution of the demulsifier' throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, to F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparativelylarge ratio of demulsifier, for instance, 115,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just suflicient to produceclean or dehydrated oil. The amount being fed at such stage is usually 110,000, 1:15 ,000,

. 1:20.000, or the like.

In many instances the oxyalkylated products herein specified as. demulsifiers can be conven' iently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of the product of Example 13b with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility char acteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 13b, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent,

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 5 Previous reference has been made to other oxyalkylating agents other than propylene oxide, such as ethylene oxide. Obviously variants can be prepared which do not depart from what is said herein but do produce modifications. The present methyl diethanolamine can be reacted with ethylene oxide in modest amounts and then subjected to oxypropylation provided that the resultant derivative is (a) water-insoluble, (b) kerosene-soluble, and (c) has present 15 to 80 alkylene oxide radicals. Needless to say, in order to have water-insolubility and kerosene-solubility the large majority must be propylene oxide.

Other variants suggest themselves as, for example, replacing propylene oxide by butylene oxide.

More specifically, one mole of the amine can be treated with 2, 4 or 6 moles of ethylene oxide and then treated with propylene oxide so as to produce a water-insoluble, kerosene-soluble oxyalkylated amine in which there are present 15 to 80 oxide radicals as previously specified. Similarly the propylene oxide can be added first and then the ethylene oxide, or random oxyalkylation "can be employed using a mixture of the two oxides. The compounds so obtained are readily esterified in the same manner as described in Part 2, preceding. Incidentally, the diols described in Part 1 or the modifications described therein can be treated with various reactants such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or monochloroacetic acid the resultant product can be further reacted with a tertiary amine such as pyridine, or the like, to give quaternary ammonium compounds. If treated with maleic anhydride to give a total ester the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulfo can be introduced also by means of a sulfating agent as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite.

I have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties of the original hydroxylated compound insofar that they are effective and valuable demulsifying agents for resolution of water-in-oil emulsions as found in the petroleum industry, as break inducers in doctor treatment of sour crude, etc.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is:

' 1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which n and n are whole numbers with the proviso that 11. plus n equals a sum varying from 15 to 80; n" is a whole number not over 2 and R is the radical of a polycarboxy acid OOOH in which n has its previous significance with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble. 2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which n and n are whole numbers with the proviso that 11. plus n equals a sum varying from 15 to 80; n is a whole number not over 2 and R is the radical of a polycarboxy acid in which n has its previous significance with the further proviso that the parent dihydroxy 20 compound prior to esterification be water-insoluble and kerosene-soluble.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

H nooowm i omoonomozNozmo oamowomooomw in which n and n are whole numbers with the proviso that 12 plus n equals a sum varying from 15 to n" is a whole number not over 2 and R is the radical of a polycarboxy acid coon R (ooomw in which n" has its previous significance; said polycarboxy acid having not more than 8 carbon atoms; with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble and kerosene-soluble.

4. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products, said hydrophile synthetic products being characterized by the following formula:

in which n and n are whole numbers with the proviso that n plus 11. equals a sum varying from 15 to 80; and R is the radical of a dicarboxy acid COOH said dicarboxy acid having not more than 8 carbon atoms; with the further proviso that the parent dihydroxy'c'ompound prior to esterification be water-insoluble and kerosene-soluble.

5. The process of claim 4 wherein the dicarboxy acid is phthalic acid.

6. The process of claim 4 wherein the dicar boxy acid is maleic acid.

"7. The process of claim 4 wherein the dicar boxy acid is succinic acid.

' 8. The process of claim 4 wherein the dicarboxy acid is citraconic acid.

9. The process of claim 4 wherein the dicarboxy acid is diglycollic acid.

' his MELVIN X DE GROQTE.

mark Witnesses to mark:

W. C. ADAMS, I. S. DE GROOTE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,243,329 De Groote et a1 May 27, 941 2,295,169 De Groote et a1. Sept. 8, 1942 2,562,878 Blair Aug. 7, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA: 